EP1420007A1 - Process for the preparation of alkali metal salts of functionalised alcohols - Google Patents

Process for the preparation of alkali metal salts of functionalised alcohols Download PDF

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Publication number
EP1420007A1
EP1420007A1 EP03103465A EP03103465A EP1420007A1 EP 1420007 A1 EP1420007 A1 EP 1420007A1 EP 03103465 A EP03103465 A EP 03103465A EP 03103465 A EP03103465 A EP 03103465A EP 1420007 A1 EP1420007 A1 EP 1420007A1
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Prior art keywords
alkali metal
alkyl
general formula
entrainer
alcohol
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German (de)
French (fr)
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EP1420007B1 (en
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Johannes Ruwwe
Klaus Stadtmüller
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Evonik Operations GmbH
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Degussa GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups

Definitions

  • the present invention relates to a method for producing solutions of Alkali metal salts of functionalized alcohols.
  • Alkali metal salts of functionalized alcohols are used in various areas, for example in the manufacture of copper-containing films in which, as in US 5,034,248 described, the sodium salt of 2-amino-1-ethanol or the sodium salt of 2-methylamino-1-ethanol is used.
  • Such alkali metal salts can also be used
  • Functionalized alcohols are used for the production of pharmaceutical products, such as Example the sodium salts of 2-ethylamino-1-ethanol and 2-amino-1-butanol, which in No. 4,235,902, or the sodium salt of 2-amino-1-ethanol, which is described in US Pat 372 974.
  • Another application of the sodium salt of 2-amino-1-ethanol is described in JP 063 061 024, where it is used for the production of polyphosphazenes becomes.
  • alkali metal salts of functionalized alcohols can be carried out, for example, by The free alcohols are reacted with alkali metals, for example in US Pat. No. 4,235,902 or described in US 4,372,974.
  • the implementation of functionalized alcohols with Alkali metals can also be used in liquid ammonia as a solvent.
  • the disadvantage this method consists in the use of very reactive metallic sodium, for The use of elaborate safety precautions must be taken.
  • alkali metal salts Another possibility for the preparation of such alkali metal salts is the implementation of free alcohols with alkali metal hydrides.
  • Such an implementation to produce the Sodium salt of 2-amino-1-ethanol is described in GB 1 341 375, this for Production of heterocycles is used.
  • the disadvantage of this method is that expensive sodium hydride must be used.
  • EP 0 518 013 describes a process for the preparation of 1-alkoxy-2-dialkylaminoethanes described.
  • the corresponding amino alcohols are used Reaction with alkali metal salts of lower alcohols in the respective alkali metal salts of functionalized alcohols.
  • the reaction is completed by the fact that the resulting lower alcohol is removed from the reaction mixture, before the working up by distillation an entrainer to remove the lower alcohol Mixture is added.
  • EP 0 518 013 also suggests as Entrainer to use the respective end products of ether synthesis. Unless one however, remember that the alkali metal salts of the functionalized alcohols are different than This procedure is forbidden to use ether formation.
  • the object of the present invention was therefore to provide a further method for Production of alkali metal salts of functionalized alcohols, which in particular in technical scale advantageous from an economic and ecological point of view to apply and, in addition, in terms of space / time yield, the method of State of the art is superior.
  • the task is solved according to the requirements.
  • the lower alcohol or the water can be distilled out of the reaction mixture in an unpredictable manner without the addition of entrainer, without side reactions taking place in the relatively more concentrated mixture, which would impair the yield and the product purity.
  • the lower amount of distillate also reduces the distillation time, which on the one hand helps to increase the space / time yield and on the other hand reduces the thermal load on the products during distillation.
  • Preferred compounds of the general formula (I) are alkali metal salts of alcohols in which M represents Li, Na, K, Rb or Cs, Y represents (C 1 -C 8 ) alkylene, X stands for NR 1 , R 1 represents H, (C 1 -C 8 ) alkyl.
  • Compounds are very particularly preferably selected from the group of the aliphatic ones Amino alcohols, e.g. B. consisting of 2-aminoethanol.
  • Alcoholate (II) can all be used in this context by the person skilled in the art for this purpose Questioning alcoholates are used.
  • This is preferably inexpensive Alkali metal salt of methanol or ethanol taken for deprotonation.
  • the alcoholates can be used as their solutions or in a solid state.
  • Preferably the salts are applied in the solid state to keep the distillant flow as low as to keep possible and to avoid further mixing of different solvents.
  • the person skilled in the art is free to choose the entrainer, provided that it is suitable for the desired purpose, ie it should have a boiling point that is greater than that of the alcohol R 2 OH or H 2 O released, or as much of the alcohol to be separated as possible or can discharge water from the reaction mixture by azeotrope formation.
  • the alcohol (II) formed or the water of reaction with or without entrainer is advantageously from a pressure range of 10 mbar to 15 bar by distillation Stripped reaction mixture.
  • the distillation is preferably carried out under reduced pressure, very particularly preferably between 100 and 500 mbar or below, depending on the technical Feasibility.
  • the essence of the present method is the fact that it is used for deprotonation Alkali alcoholate or the alkali hydroxide after the reaction as low-boiling alcohol or Water is first distilled off from the reaction mixture without the addition of an entrainer become. It is up to the person skilled in the art to what degree this first distillation is driven, but here it is preferably based on the economy of the Process or the available product purity, which should be as high as possible. Preferably 10-90 vol .-% of the alcohol (II) or water released without The entrainer is distilled off before the corresponding entrainer is distilled be added to the reaction mixture. Under the above premises appears the greatest possible removal of the components to be distilled off (water, However, alcohol) is particularly preferred in the first distillation step.
  • the present invention works by making it solid Adds alkali alcoholate or alkali hydroxide to a functionalized alcohol and begins to take the resulting water or alcohol from the mixture to distill off under reduced pressure.
  • Add entrainer to the reaction mixture and distill until the water of reaction or the alcohol formed is reduced to an acceptable level (often below 100 ppm).
  • the yield of product and its purity are always> 90% to 99%.
  • Functionalized alcoholates present in solution can be used in subsequent reactions such as B. an ether formation with alkyl halides.
  • (C 1 -C 8 ) -alkylene means a (C 1 -C 8 ) -alkyl radical which is bonded to the molecule in question via two valences. These radicals can be reacted one or more times with (C 1 -C 8 ) alkoxy, (C 1 -C 8 ) haloalkyl, halogen, NH 2 , NH (C 1 -C 8 ) alkyl, N [(C 1 -C 8 ) -alkyl] 2 or S- (C 1 -C 8 ) -alkyl.
  • a (C 2 -C 8 ) alkenyl is a (C 1 -C 8 ) alkyl radical as shown above, with the exception of methyl, which has at least one double bond.
  • (C 2 -C 8 ) -alkynyl is to be understood as a (C 1 -C 8 ) -alkyl radical as shown above, with the exception of methyl, which has at least one triple bond.
  • Cycloalkyl means cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl residues etc. These can be substituted with one or more halogens and / or residues containing N, O, P, S atoms and / or have N, O, P, S atom-containing radicals in the ring, such as.
  • B. 1-, 2-, 3-, 4-piperidyl, 1-, 2-, 3-pyrrolidinyl, 2-, 3-tetrahydrofuryl or 2-, 3-, 4-morpholinyl.
  • a (C 6 -C 18 ) aryl radical is understood to mean an aromatic radical with 6 to 18 C atoms.
  • these include compounds such as phenyl, naphthyl, anthryl, phenanthryl or biphenyl radicals. This can be repeated one or more times with (C 1 -C 8 ) alkoxy, (C 1 -C 8 ) haloalkyl, halogen, NH 2 , S- (C 1 -C 8 ) alkyl, (C 1 -C 8 ) -Acyl, (C 1 -C 8 ) alkyl.
  • a (C 7 -C 19 ) aralkyl radical is a (C 6 -C 18 ) aryl radical bonded to the molecule via a (C 1 -C 8 ) alkyl radical.
  • (C 1 -C 8 ) alkoxy is a (C 1 -C 8 ) alkyl radical bonded to the molecule under consideration via an oxygen atom.
  • (C 1 -C 8 ) haloalkyl is a (C 1 -C 8 ) alkyl radical substituted by one or more halogen atoms.
  • a (C 3 -C 18 ) heteroaryl radical denotes a five-, six- or seven-membered aromatic ring system composed of 3 to 18 carbon atoms, which heteroatoms such as, for. B. has nitrogen, oxygen or sulfur in the ring.
  • heteroaromatics are in particular radicals, such as 1-, 2-, 3-furyl, 1-, 2-, 3-pyrrolyl, 1-, 2-, 3-thienyl, 2-, 3-, 4-pyridyl, 2 -, 3-, 4-, 5-, 6-, 7-indolyl, 3-, 4-, 5-pyrazolyl, 2-, 4-, 5-imidazolyl, acridinyl, quinolinyl, phenanthridinyl, 2-, 4-, 5-, 6-pyrimidinyl.
  • a (C 4 -C 19 ) heteroaralkyl is understood to mean a heteroaromatic system corresponding to the (C 7 -C 19 ) aralkyl radical.
  • Halogen, fluorine, chlorine, bromine and iodine are suitable.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Production of solutions of alkali metal salts (I) of functionalized alcohols (II) in a solvent mixture including (II), by reacting (II) with an alkali metal alkoxide or hydroxide (III), comprises distilling off part of the released alkanol or water without adding an entrainer and then distilling off the rest using another organic solvent as entrainer. Production of solutions of alkali metal salts of formula MOYXR1 (I) by reacting a functionalized alcohol of formula HOYXR1 (II) with an alkali metal alkoxide or hydroxide of formula MOR2 (III) to form a solution of (I) in a solvent mixture including (II), comprises distilling off part of the released alkanol or water without adding an entrainer and then distilling off the rest using another organic solvent as entrainer. M = Li, Na, K, Rb or Cs; Y = 1-8C alkylene; X = O, S or NR1; R1 = H, 1-8C alkyl, 2-8C alkenyl, 2-8C alkynyl, 3-8C cycloalkyl, 6-18C aryl, 7-19C aralkyl, 3-18C heteroaryl or 4-19C heteroaralkyl, where cycloalkyl, aryl and heteroaryl are optionally substituted by 1-3 of 1-8C alkyl; and R2 = H, Me, Et, Pr, i-Pr, s-Bu, i-Bu or t-Bu.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Lösungen von Alkalimetallsalzen funktionalisierter Alkohole.The present invention relates to a method for producing solutions of Alkali metal salts of functionalized alcohols.

Alkalimetallsalze funktionalisierter Alkohole finden Anwendung in verschiedenen Bereichen, zum Beispiel bei der Herstellung von kupferhaltigen Filmen, bei denen, wie in US 5 034 248 beschrieben, das Natriumsalz des 2-Amino-1-ethanols oder das Natriumsalz des 2-Methylamino-1-ethanols eingesetzt wird. Ebenfalls können solche Alkalimetallsalze funktionalisierter Alkohole zur Herstellung pharmazeutischer Produkte dienen, wie zum Beispiel die Natriumsalze des 2-Ethylamino-1-ethanols und des 2-Amino-1-butanols, welche in US 4 235 902 beschrieben sind, oder das Natriumsalz des 2-Amino-1-ethanols, welches in US 4 372 974 beschrieben ist. Eine weitere Anwendung des Natriumsalzes des 2-Amino-1-ethanols ist in JP 063 061 024 beschrieben, wo es zur Herstellung von Polyphosphazenen eingesetzt wird.Alkali metal salts of functionalized alcohols are used in various areas, for example in the manufacture of copper-containing films in which, as in US 5,034,248 described, the sodium salt of 2-amino-1-ethanol or the sodium salt of 2-methylamino-1-ethanol is used. Such alkali metal salts can also be used Functionalized alcohols are used for the production of pharmaceutical products, such as Example the sodium salts of 2-ethylamino-1-ethanol and 2-amino-1-butanol, which in No. 4,235,902, or the sodium salt of 2-amino-1-ethanol, which is described in US Pat 372 974. Another application of the sodium salt of 2-amino-1-ethanol is described in JP 063 061 024, where it is used for the production of polyphosphazenes becomes.

Die Herstellung von Alkalimetallsalzen funktionalisierter Alkohole kann beispielsweise durch Umsetzung der freien Alkohole mit Alkalimetallen erfolgen, wie zum Beispiel in US 4 235 902 oder in US 4 372 974 beschrieben. Die Umsetzung von funktionalisierten Alkoholen mit Alkalimetallen kann ebenfalls in flüssigem Ammoniak als Lösemittel erfolgen. Der Nachteil dieser Verfahren besteht in der Verwendung des sehr reaktiven metallischen Natriums, für dessen Einsatz aufwändige Sicherheitsvorkehrungen getroffen werden müssen.The production of alkali metal salts of functionalized alcohols can be carried out, for example, by The free alcohols are reacted with alkali metals, for example in US Pat. No. 4,235,902 or described in US 4,372,974. The implementation of functionalized alcohols with Alkali metals can also be used in liquid ammonia as a solvent. The disadvantage this method consists in the use of very reactive metallic sodium, for The use of elaborate safety precautions must be taken.

Eine weitere Möglichkeit zur Darstellung solcher Alkalimetallsalze besteht in der Umsetzung von freien Alkoholen mit Alkalimetallhydriden. Eine solche Umsetzung zur Herstellung des Natriumsalzes des 2-Amino-1-ethanols ist in GB 1 341 375 beschrieben, wobei dieses zur Herstellung von Heterocyclen verwendet wird. Nachteilig an diesem Verfahren ist, dass das teure Natriumhydrid eingesetzt werden muss.Another possibility for the preparation of such alkali metal salts is the implementation of free alcohols with alkali metal hydrides. Such an implementation to produce the Sodium salt of 2-amino-1-ethanol is described in GB 1 341 375, this for Production of heterocycles is used. The disadvantage of this method is that expensive sodium hydride must be used.

Es besteht weiterhin die Möglichkeit, funktionalisierte Alkohole mit Alkalimetallamiden oder metallorganischen Verbindungen der Alkalimetalle umzusetzen, um die Alkalimetallsalze der funktionalisierten Alkohole zu erhalten. Solche Umsetzungen sind in US 5 629 452 beschrieben, wobei Diphenylmethylkalium, Diphenylmethylnatrium oder Natriumamid eingesetzt wird. Diese Verbindungen sind aufwändig herzustellen oder aber teuer. Desweiteren verbleibt, zumindest im Fall des Diphenylmethylkaliums und des Diphenylmethylnatriums, nach der Umsetzung das entstehende Diphenylmethan in der erhaltenen Reaktionsmischung, wenn kein weiterer Aufarbeitungsschritt durchgeführt wird.There is also the possibility of functionalized alcohols with alkali metal amides or implement organometallic compounds of the alkali metals to the alkali metal salts to get functionalized alcohols. Such implementations are in US 5,629,452 described, diphenylmethyl potassium, diphenylmethyl sodium or sodium amide is used. These connections are difficult to manufacture or expensive. Furthermore remains, at least in the case of diphenylmethyl potassium and diphenylmethyl sodium, after the reaction, the diphenylmethane formed in the reaction mixture obtained, if no further processing step is carried out.

In der EP 0 518 013 wird ein Verfahren zur Herstellung von 1-Alkoxy-2-dialkylaminoethanen beschrieben. Im ersten Schritt werden dabei die entsprechenden Aminoalkohole durch Umsetzen mit Alkalisalzen niederer Alkohole in die jeweiligen Alkalimetallsalze der funktionalisierten Alkohole überführt. Die Reaktion wird dadurch vervollständigt, dass der entstehende niedere Alkohol aus dem Reaktionsgemisch entfernt wird, wobei vor der destillativen Aufarbeitung ein Schleppmittel zur Entfernung des niederen Alkohols zur Mischung hinzugegeben wird. Alternativ schlägt die EP 0 518 013 jedoch auch vor, als Schleppmittel die jeweiligen Endprodukte der Ethersynthese heranzuziehen. Sofern man jedoch daran denkt, die Alkalimetallsalze der funktionalisierten Alkohole anders als zur Etherbildung einzusetzen, verbietet sich dieses Vorgehen.EP 0 518 013 describes a process for the preparation of 1-alkoxy-2-dialkylaminoethanes described. In the first step, the corresponding amino alcohols are used Reaction with alkali metal salts of lower alcohols in the respective alkali metal salts of functionalized alcohols. The reaction is completed by the fact that the resulting lower alcohol is removed from the reaction mixture, before the working up by distillation an entrainer to remove the lower alcohol Mixture is added. Alternatively, EP 0 518 013 also suggests as Entrainer to use the respective end products of ether synthesis. Unless one however, remember that the alkali metal salts of the functionalized alcohols are different than This procedure is forbidden to use ether formation.

Aufgabe der vorliegenden Erfindung war daher die Angabe eines weiteren Verfahrens zur Herstellung von Alkalimetallsalzen funktionalisierter Alkohole, welches insbesondere im technischen Maßstab unter ökonomischen und ökologischen Gesichtspunkten vorteilhaft anzuwenden und darüber hinaus in Bezug auf die Raum/Zeit-Ausbeute den Verfahren des Standes der Technik überlegen ist.The object of the present invention was therefore to provide a further method for Production of alkali metal salts of functionalized alcohols, which in particular in technical scale advantageous from an economic and ecological point of view to apply and, in addition, in terms of space / time yield, the method of State of the art is superior.

Die Aufgabe wird anspruchsgemäß gelöst.The task is solved according to the requirements.

Dadurch, dass man in einem Verfahren zur Herstellung von Lösungen von Alkalimetallsalzen der allgemeinen Formel (I) MOYXR1 worin
M steht für Li, Na, K, Rb oder Cs,
Y steht für (C1-C8)-Alkylen,
X steht für O, S, NR1,
R1 steht für H, (C1-C8)-Alkyl, (C2-C8)-Alkenyl, (C2-C8)-Alkinyl, (C3-C8)-Cycloalkyl, (C6-C18)-Aryl, (C7-C19)-Aralkyl, (C3-C18)-Heteroaryl, (C4-C19)-Heteroaralkyl, ((C1-C8)-Alkyl)1-3-(C3-C8)-Cycloalkyl, ((C1-C8)-Alkyl)1-3-(C6-C18)-Aryl, ((C1-C8)-Alkyl)1-3-(C3-C18)-Heteroaryl, in einem Lösemittelgemisch aufweisend den korrespondierenden Alkohol der allgemeinen Formel (I) die Umsetzung des korrespondierenden Alkohols der allgemeinen Formel (I) mit dem entsprechenden Alkalimetallsalz eines Alkohols der allgemeinen Formel (II) MOR2 worin
M die oben angegebene Bedeutung annimmt und
R2 bedeutet Methyl, Ethyl, Propyl, Isopropyl, sec-, Iso- oder tert.-Butyl, durchführt, oder die Umsetzung des korrespondierenden Alkohols der allgemeinen Formel (I) mit dem entsprechenden Alkalimetallhydroxid betreibt, wobei zuerst eine Teilmenge des freigesetzten Alkohols der allgemeinen Formel (II) oder des freigesetzten Wassers ohne Zusatz eines Schleppmittels und anschließend die Restmenge unter Zuhilfenahme mindestens eines weiteren organischen Lösemittels als Schleppmittel aus der Lösung destilliert wird, gelangt man völlig überraschend, dafür aber nicht minder vorteilhaft, zur Lösung der gestellten Aufgabe. In unvorhersehbarer Weise lässt sich der niedere Alkohol bzw. das Wasser aus der Reaktionsmischung ohne Schleppmittelzugabe bis zu einem gewissen Teil herausdestillieren, ohne dass Nebenreaktionen in der relativ konzentrierteren Mischung ablaufen, die die Ausbeute und die Produktreinheit beeinträchtigen würden. Durch die geringere Destillatmenge verringert sich darüber hinaus die Destillationszeit, was einerseits die Raum/Zeit-Ausbeute steigern hilft und andererseits die thermische Belastung der Produkte bei der Destillation verringert.The fact that in a process for the preparation of solutions of alkali metal salts of the general formula (I) MOYXR 1 wherein
M stands for Li, Na, K, Rb or Cs,
Y represents (C 1 -C 8 ) alkylene,
X stands for O, S, NR 1 ,
R 1 represents H, (C 1 -C 8 ) alkyl, (C 2 -C 8 ) alkenyl, (C 2 -C 8 ) alkynyl, (C 3 -C 8 ) cycloalkyl, (C 6 - C 18 ) aryl, (C 7 -C 19 ) aralkyl, (C 3 -C 18 ) heteroaryl, (C 4 -C 19 ) heteroaralkyl, ((C 1 -C 8 ) alkyl) 1-3 - (C 3 -C 8 ) cycloalkyl, ((C 1 -C 8 ) alkyl) 1-3 - (C 6 -C 18 ) aryl, ((C 1 -C 8 ) alkyl) 1-3 - (C 3 -C 18 ) heteroaryl, in a solvent mixture comprising the corresponding alcohol of the general formula (I), the reaction of the corresponding alcohol of the general formula (I) with the corresponding alkali metal salt of an alcohol of the general formula (II) MOR 2 wherein
M assumes the meaning given above and
R 2 means methyl, ethyl, propyl, isopropyl, sec-, iso- or tert-butyl, or the reaction of the corresponding alcohol of the general formula (I) with the corresponding alkali metal hydroxide, first of all a portion of the alcohol released general formula (II) or the water released without the addition of an entrainer and then the remaining amount is distilled from the solution with the aid of at least one other organic solvent as entrainer, one arrives completely surprisingly, but no less advantageous, to solve the task. To a certain extent, the lower alcohol or the water can be distilled out of the reaction mixture in an unpredictable manner without the addition of entrainer, without side reactions taking place in the relatively more concentrated mixture, which would impair the yield and the product purity. The lower amount of distillate also reduces the distillation time, which on the one hand helps to increase the space / time yield and on the other hand reduces the thermal load on the products during distillation.

Als bevorzugte Verbindungen der allgemeinen Formel (I) werden Alkalimetallsalze von Alkoholen, in denen M steht für
Li, Na, K, Rb oder Cs,
Y steht für (C1-C8)-Alkylen,
X steht für NR1,
R1 steht für H, (C1-C8)-Alkyl, verwendet.Preferred compounds of the general formula (I) are alkali metal salts of alcohols in which M represents
Li, Na, K, Rb or Cs,
Y represents (C 1 -C 8 ) alkylene,
X stands for NR 1 ,
R 1 represents H, (C 1 -C 8 ) alkyl.

Ganz besonders bevorzugt sind Verbindungen ausgewählt aus der Gruppe der aliphatischen Amino-Alkohole, z. B. bestehend aus 2-Amino-ethanol.Compounds are very particularly preferably selected from the group of the aliphatic ones Amino alcohols, e.g. B. consisting of 2-aminoethanol.

Als Alkoholat (II) können im oben genannten Rahmen alle dem Fachmann für diesen Zweck in Frage kommenden Alkoholate herangezogen werden. Vorzugsweise wird das kostengünstige Alkalimetallsalz des Methanols oder Ethanols zur Deprotonierung genommen. Die Alkoholate können dabei als ihre Lösungen oder in festem Zustand eingesetzt werden. Vorzugsweise werden die Salze in festem Zustand angewandt, um den Destillationsmittelstrom so gering wie möglich zu halten und eine weitere Vermengung unterschiedlicher Lösemittel zu vermeiden.Alcoholate (II) can all be used in this context by the person skilled in the art for this purpose Questioning alcoholates are used. This is preferably inexpensive Alkali metal salt of methanol or ethanol taken for deprotonation. The alcoholates can be used as their solutions or in a solid state. Preferably the salts are applied in the solid state to keep the distillant flow as low as to keep possible and to avoid further mixing of different solvents.

Prinzipiell ist der Fachmann frei in der Wahl der Schleppmittel, sofern sie sich zum gewünschten Zweck eignen, d. h. sie sollten möglichst einen Siedepunkt besitzen, der größer als der des freigesetzten Alkohols R2OH bzw. H2O ist, oder möglichst viel des abzutrennenden Alkohols oder Wassers aus dem Reaktionsgemisch durch Azeotropbildung ausschleusen können. Darüber hinaus ist es vorteilhaft, ein Schleppmittel zu verwenden, welches sich als inert erweist, damit Reste dieses Schleppmittels bedenkenlos im Reaktionsgemisch verbleiben können, ohne dass eine folgende Reaktion der Alkalimetallsalze der funktionalisierten Alkohole negativ beeinträchtigt wird.In principle, the person skilled in the art is free to choose the entrainer, provided that it is suitable for the desired purpose, ie it should have a boiling point that is greater than that of the alcohol R 2 OH or H 2 O released, or as much of the alcohol to be separated as possible or can discharge water from the reaction mixture by azeotrope formation. In addition, it is advantageous to use an entrainer which proves to be inert, so that residues of this entrainer can safely remain in the reaction mixture without a subsequent reaction of the alkali metal salts of the functionalized alcohols being adversely affected.

Als weiteres organisches Lösemittel kann ein Schleppmittel verwendet werden, das ausgewählt ist aus der Gruppe, bestehend aus linearen oder cyclischen aliphatischen Kohlenwasserstoffen, aromatischen Kohlenwasserstoffen, Verbindungen des Typs der allgemeinen Formel (III) R1(XY)nXR1 worin
n = 1 oder 2 sein kann,
R1 jeweils unabhängig voneinander, X jeweils unabhängig voneinander und Y die in Anspruch 1 angegebene Bedeutung annehmen,
und Alkoholen der allgemeinen Formel (IV) R3OH worin
R3 = (C4-C8)-Alkyl, (C2-C8)-Alkenyl, (C2-C8)-Alkinyl oder (C3-C8)-Cycloalkyl bedeuten.As an additional organic solvent, an entrainer can be used which is selected from the group consisting of linear or cyclic aliphatic hydrocarbons, aromatic hydrocarbons, compounds of the type of the general formula (III) R 1 (XY) n XR 1 wherein
n = 1 or 2,
R 1 in each case independently of one another, X in each case independently of one another and Y assume the meaning given in claim 1,
and alcohols of the general formula (IV) R 3 OH wherein
R 3 = (C 4 -C 8 ) alkyl, (C 2 -C 8 ) alkenyl, (C 2 -C 8 ) alkynyl or (C 3 -C 8 ) cycloalkyl.

Bevorzugt ist die Verwendung von Schleppmitteln aus der Gruppe bestehend aus Toluol, Xylol, Benzol, Hexan, Heptan, Cyclohexan, Methylcyclohexan, oder weniger acide Alkohole wie z. B. n-Butanol oder Ethylenglykol oder Ethylendiamin oder Diethylentriamin.Preference is given to using entraining agents from the group consisting of toluene, Xylene, benzene, hexane, heptane, cyclohexane, methylcyclohexane, or less acidic alcohols such as B. n-butanol or ethylene glycol or ethylenediamine or diethylenetriamine.

Der entstehende Alkohol (II) bzw. das Reaktionswasser mit bzw. ohne Schleppmittel wird vorteilhafterweise in einem Druckbereich von 10 mbar bis 15 bar destillativ aus der Reaktionsmischung abgezogen. Bevorzugt erfolgt die Destillation jedoch unter Unterdruck, ganz besonders bevorzugt zwischen 100 und 500 mbar oder darunter, je nach technischer Machbarkeit.The alcohol (II) formed or the water of reaction with or without entrainer is advantageously from a pressure range of 10 mbar to 15 bar by distillation Stripped reaction mixture. However, the distillation is preferably carried out under reduced pressure, very particularly preferably between 100 and 500 mbar or below, depending on the technical Feasibility.

Kern des vorliegenden Verfahrens ist die Tatsache, dass das zur Deprotonierung eingesetzte Alkalialkoholat oder das Alkalihydroxid nach der Umsetzung als leichtsiedender Alkohol bzw. Wasser aus dem Reaktionsgemisch zuerst ohne Zusatz eines Schleppmittels abdestilliert werden. Es bleibt dem Fachmann überlassen, bis zu welchem Grad diese erste Destillation getrieben wird, doch orientiert man sich hier vorzugsweise an der Wirtschaftlichkeit des Verfahrens bzw. der erhältlichen Produktreinheit, die möglichst hoch ausfallen sollte. Vorzugsweise werden 10 - 90 Vol.-% des freigesetzten Alkohols (II) oder Wassers ohne Schleppmittel abdestilliert, bevor zur weiteren Destillation die entsprechenden Schleppmittel zum Reaktionsgemisch hinzugegeben werden. Unter den oben genannten Prämissen erscheint eine möglichst weitgehende Entfernung der abzudestillierenden Bestandteile (Wasser, Alkohol) im ersten Destillationsschritt jedoch als besonders bevorzugt.The essence of the present method is the fact that it is used for deprotonation Alkali alcoholate or the alkali hydroxide after the reaction as low-boiling alcohol or Water is first distilled off from the reaction mixture without the addition of an entrainer become. It is up to the person skilled in the art to what degree this first distillation is driven, but here it is preferably based on the economy of the Process or the available product purity, which should be as high as possible. Preferably 10-90 vol .-% of the alcohol (II) or water released without The entrainer is distilled off before the corresponding entrainer is distilled be added to the reaction mixture. Under the above premises appears the greatest possible removal of the components to be distilled off (water, However, alcohol) is particularly preferred in the first distillation step.

Im Allgemeinen geht man bei der vorliegenden Erfindung so vor, dass man festes Alkalialkoholat oder Alkalihydroxid zu einem funktionalisierten Alkohol hinzufügt und beginnt, das entstehende Wasser oder den entstehenden Alkohol aus der Mischung unter vermindertem Druck abzudestillieren. Ab einem bestimmten Punkt, der durch Routineexperimente im Hinblick auf oben genannte Sachverhalte zu ermitteln ist, gibt man das Schleppmittel zur Reaktionsmischung hinzu und destilliert solange, bis das Reaktionswasser oder der gebildete Alkohol zu einem erträglichen Maß vermindert ist (häufig unter 100 ppm). Die Ausbeute an Produkt und dessen Reinheit liegen dabei immer > 90 % bis 99 %. Die in Lösung vorliegenden funktionalisierten Alkoholate können so in nachfolgenden Reaktionen wie z. B. einer Etherbildung mit Alkylhalogeniden eingesetzt werden. Aufgrund der Tatsache, dass Reinheit und Ausbeute an Verbindungen der Formel (I) derart gut sind, können auch Nachfolgeprodukte, wie die ins Auge gefassten Ether, in hohen Ausbeuten und entsprechend guten Reinheiten gewonnen werden. Dieses, kombiniert mit einer höheren Raum/Zeit-Ausbeute, ist für den Fachmann im Hinblick auf den Stand der Technik besonders überraschend.In general, the present invention works by making it solid Adds alkali alcoholate or alkali hydroxide to a functionalized alcohol and begins to take the resulting water or alcohol from the mixture to distill off under reduced pressure. At some point passing through Routine experiments to be determined with regard to the above-mentioned facts are given Add entrainer to the reaction mixture and distill until the water of reaction or the alcohol formed is reduced to an acceptable level (often below 100 ppm). The yield of product and its purity are always> 90% to 99%. In the Functionalized alcoholates present in solution can be used in subsequent reactions such as B. an ether formation with alkyl halides. Due to the fact, that purity and yield of compounds of the formula (I) are so good can also Successor products, such as the envisaged ethers, in high yields and accordingly good purities can be obtained. This, combined with a higher space / time yield, is special for the person skilled in the art with regard to the prior art surprised.

Als (C1-C8)-Alkyl sind anzusehen Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, sec-Butyl, tert-Butyl, Pentyl, Hexyl, Heptyl oder Octyl samt aller Bindungsisomeren.As (C 1 -C 8 ) alkyl methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl or octyl together with all binding isomers are to be regarded.

(C1-C8)-Alkylen bedeutet einen (C1-C8)-Alkylrest, der über zwei Valenzen an das in Frage stehende Molekül gebunden ist. Diese Reste können einfach oder mehrfach mit (C1-C8)-Alkoxy, (C1-C8)-Haloalkyl, Halogen, NH2, NH(C1-C8)-Alkyl, N[(C1-C8)-Alkyl]2 oder S-(C1-C8)-Alkyl substituiert sein.(C 1 -C 8 ) -alkylene means a (C 1 -C 8 ) -alkyl radical which is bonded to the molecule in question via two valences. These radicals can be reacted one or more times with (C 1 -C 8 ) alkoxy, (C 1 -C 8 ) haloalkyl, halogen, NH 2 , NH (C 1 -C 8 ) alkyl, N [(C 1 -C 8 ) -alkyl] 2 or S- (C 1 -C 8 ) -alkyl.

Als (C2-C8)-Alkenyl ist ein wie oben dargestellter (C1-C8)-Alkyl-Rest mit Ausnahme von Methyl zu verstehen, der mindestens eine Doppelbindung aufweist.A (C 2 -C 8 ) alkenyl is a (C 1 -C 8 ) alkyl radical as shown above, with the exception of methyl, which has at least one double bond.

Unter (C2-C8)-Alkinyl ist ein wie oben dargestellter (C1-C8)-Alkyl-Rest mit Ausnahme von Methyl zu verstehen, der mindestens eine Dreifachbindung aufweist.(C 2 -C 8 ) -alkynyl is to be understood as a (C 1 -C 8 ) -alkyl radical as shown above, with the exception of methyl, which has at least one triple bond.

Unter (C1-C8)-Acyl versteht man einen über eine -C=O-Funktion ans Molekül gebundenen (C1-C8)-Alkyl-Rest. (C 1 -C 8 ) -acyl is understood to mean a (C 1 -C 8 ) -alkyl radical bonded to the molecule via a -C = O function.

Unter (C3-C8)-Cycloalkyl versteht man Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl bzw. Cycloheptylreste etc. Diese können mit einem oder mehreren Halogenen und/oder N-, O-, P-, S-atomhaltigen Resten substituiert sein und/oder N-, O-, P-, S-atomhaltige Reste im Ring aufweisen, wie z. B. 1-, 2-, 3-, 4-Piperidyl, 1-, 2-, 3-Pyrrolidinyl, 2-, 3-Tetrahydrofuryl oder 2-, 3-, 4-Morpholinyl. Dieser kann einfach oder mehrfach mit (C1-C8)-Alkoxy, (C1-C8)-Haloalkyl, Halogen, NH2, S-(C1-C8)-Alkyl, (C1-C8)-Acyl, (C1-C8)-Alkyl substituiert sein.(C 3 -C 8 ) Cycloalkyl means cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl residues etc. These can be substituted with one or more halogens and / or residues containing N, O, P, S atoms and / or have N, O, P, S atom-containing radicals in the ring, such as. B. 1-, 2-, 3-, 4-piperidyl, 1-, 2-, 3-pyrrolidinyl, 2-, 3-tetrahydrofuryl or 2-, 3-, 4-morpholinyl. This can be repeated one or more times with (C 1 -C 8 ) alkoxy, (C 1 -C 8 ) haloalkyl, halogen, NH 2 , S- (C 1 -C 8 ) alkyl, (C 1 -C 8 ) -Acyl, (C 1 -C 8 ) alkyl.

Unter einem (C6-C18)-Arylrest wird ein aromatischer Rest mit 6 bis 18 C-Atomen verstanden. Insbesondere zählen hierzu Verbindungen wie Phenyl-, Naphthyl-, Anthryl-, Phenanthryl- oder Biphenylreste. Dieser kann einfach oder mehrfach mit (C1-C8)-Alkoxy, (C1-C8)-Haloalkyl, Halogen, NH2, S-(C1-C8)-Alkyl, (C1-C8)-Acyl, (C1-C8)-Alkyl substituiert sein.A (C 6 -C 18 ) aryl radical is understood to mean an aromatic radical with 6 to 18 C atoms. In particular, these include compounds such as phenyl, naphthyl, anthryl, phenanthryl or biphenyl radicals. This can be repeated one or more times with (C 1 -C 8 ) alkoxy, (C 1 -C 8 ) haloalkyl, halogen, NH 2 , S- (C 1 -C 8 ) alkyl, (C 1 -C 8 ) -Acyl, (C 1 -C 8 ) alkyl.

Ein (C7-C19)-Aralkylrest ist ein über einen (C1-C8)-Alkylrest an das Molekül gebundener (C6-C18)-Arylrest.A (C 7 -C 19 ) aralkyl radical is a (C 6 -C 18 ) aryl radical bonded to the molecule via a (C 1 -C 8 ) alkyl radical.

(C1-C8)-Alkoxy ist ein über ein Sauerstoffatom an das betrachtete Molekül gebundener (C1-C8)-Alkyl-Rest.(C 1 -C 8 ) alkoxy is a (C 1 -C 8 ) alkyl radical bonded to the molecule under consideration via an oxygen atom.

(C1-C8)-Haloalkyl ist ein mit einem oder mehreren Halogenatomen substituierter (C1-C8)-Alkyl-Rest.(C 1 -C 8 ) haloalkyl is a (C 1 -C 8 ) alkyl radical substituted by one or more halogen atoms.

Ein (C3-C18)-Heteroarylrest bezeichnet im Rahmen der Erfindung ein fünf-, sechs- oder siebengliedriges aromatisches Ringsystem aus 3 bis 18 C-Atomen, welches Heteroatome wie z. B. Stickstoff, Sauerstoff oder Schwefel im Ring aufweist. Als solche Heteroaromaten werden insbesondere Reste angesehen, wie 1-, 2-, 3-Furyl, 1-, 2-, 3-Pyrrolyl, 1-,2-,3-Thienyl, 2-, 3-, 4-Pyridyl, 2 -, 3-, 4-, 5-, 6-, 7-Indolyl, 3-, 4-, 5-Pyrazolyl, 2-, 4-, 5-Imidazolyl, Acridinyl, Chinolinyl, Phenanthridinyl, 2-, 4-, 5-, 6-Pyrimidinyl. Dieser kann einfach oder mehrfach mit (C1-C8)-Alkoxy, (C1-C8)-Haloalkyl, Halogen, NH2, S-(C1-C8)-Alkyl, (C1-C8)-Acyl oder (C1-C8)-Alkyl substituiert sein.In the context of the invention, a (C 3 -C 18 ) heteroaryl radical denotes a five-, six- or seven-membered aromatic ring system composed of 3 to 18 carbon atoms, which heteroatoms such as, for. B. has nitrogen, oxygen or sulfur in the ring. Such heteroaromatics are in particular radicals, such as 1-, 2-, 3-furyl, 1-, 2-, 3-pyrrolyl, 1-, 2-, 3-thienyl, 2-, 3-, 4-pyridyl, 2 -, 3-, 4-, 5-, 6-, 7-indolyl, 3-, 4-, 5-pyrazolyl, 2-, 4-, 5-imidazolyl, acridinyl, quinolinyl, phenanthridinyl, 2-, 4-, 5-, 6-pyrimidinyl. This can be repeated one or more times with (C 1 -C 8 ) alkoxy, (C 1 -C 8 ) haloalkyl, halogen, NH 2 , S- (C 1 -C 8 ) alkyl, (C 1 -C 8 ) -Acyl or (C 1 -C 8 ) alkyl may be substituted.

Unter einem (C4-C19)-Heteroaralkyl wird ein dem (C7-C19)-Aralkylrest entsprechendes heteroaromatisches System verstanden.A (C 4 -C 19 ) heteroaralkyl is understood to mean a heteroaromatic system corresponding to the (C 7 -C 19 ) aralkyl radical.

Als Halogene kommen Fluor, Chlor, Brom und Iod in Frage.Halogen, fluorine, chlorine, bromine and iodine are suitable.

Beispiele:Examples:

Die folgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern.The following examples are intended to explain the subject matter of the invention in more detail.

Beispiel 1 (erfindungsgemäß): Example 1

Benötigt wird das Natriumsalz des 2-Amino-1-ethanols in einem Gemisch aus 2-Amino-1-ethanol und n-Butanol, es ist erforderlich, dass der Methanolgehalt möglichst klein ist:

  • 350 g (5,73 mol) 2-Amino-1-ethanol werden mit 92 g (1,70 mol) festem Natrium-methanolat versetzt. Bei einem Druck von 400 mbar werden 46 g Methanol abdestilliert, was ca. 84 % der theoretischen Menge entspricht. Anschließend werden 199 g n-Butanol zugegeben und bei einem Druck von 150 mbar weitere 115 g Destillat bis zu einer Sumpftemperatur von 110 °C abgenommen. Es kann eine Methanol-Konzentration von nur noch 0,013 % festgestellt werden.
    • The sodium salt of 2-amino-1-ethanol is required in a mixture of 2-amino-1-ethanol and n-butanol. It is necessary that the methanol content is as low as possible:
  • 350 g (5.73 mol) of 2-amino-1-ethanol are mixed with 92 g (1.70 mol) of solid sodium methanolate. At a pressure of 400 mbar, 46 g of methanol are distilled off, which corresponds to approximately 84% of the theoretical amount. 199 g of n-butanol are then added, and a further 115 g of distillate are removed at a pressure of 150 mbar up to a bottom temperature of 110.degree. A methanol concentration of only 0.013% can be determined.

    • Beispiel 2 (erfindungsgemäß): Example 2 (According to the Invention)

    Benötigt wird das Natriumsalz des 2-Amino-1-butanols in einem Gemisch aus 2-Amino-1-butanol und Toluol, es ist erforderlich, dass der Methanolgehalt möglichst klein ist:

  • 350 g (3,93 mol) 2-Amino-1-butanol werden mit 92 g (1,70 mol) festem Natrium-methanolat versetzt. Bei einem Druck von 400 mbar werden 47 g Methanol abdestilliert, was ca. 84 % der theoretischen Menge entspricht. Anschließend werden 200 g Toluol zugegeben und bei einem Druck von 150 mbar weitere 120 g Destillat bis zu einer Sumpftemperatur von 120 °C abgenommen. Es kann eine Methanol-Konzentration von nur noch 0,011 % festgestellt werden.
    • The sodium salt of 2-amino-1-butanol is required in a mixture of 2-amino-1-butanol and toluene. It is necessary that the methanol content is as low as possible:
  • 350 g (3.93 mol) of 2-amino-1-butanol are mixed with 92 g (1.70 mol) of solid sodium methanolate. At a pressure of 400 mbar, 47 g of methanol are distilled off, which corresponds to approximately 84% of the theoretical amount. 200 g of toluene are then added and a further 120 g of distillate are removed at a pressure of 150 mbar up to a bottom temperature of 120.degree. A methanol concentration of only 0.011% can be determined.

    • Beispiel 3 (erfindungsgemäß): Example 3

    Benötigt wird das Natriumsalz des 2-Amino-1-butanols in einem Gemisch aus 2-Amino-1-butanol und n-Butanol, es ist erforderlich, dass der Methanolgehalt möglichst klein ist:

  • 350g (3,93 mol) 2-Amino-1-butanol werden mit 92 g (1,70 mol) festem Natrium-methanolat versetzt. Bei einem Druck von 400 mbar werden 47 g Methanol abdestilliert, was ca. 84 % der theoretischen Menge entspricht. Anschließend werden 205 g n-Butanol zugegeben und bei einem Druck von 150 mbar weitere 120 g Destillat bis zu einer Sumpftemperatur von 123 °C abgenommen. Es kann eine Methanol-Konzentration von nur noch 0,011 % festgestellt werden.
    • The sodium salt of 2-amino-1-butanol is required in a mixture of 2-amino-1-butanol and n-butanol. It is necessary that the methanol content is as low as possible:
  • 350 g (3.93 mol) of 2-amino-1-butanol are mixed with 92 g (1.70 mol) of solid sodium methanolate. At a pressure of 400 mbar, 47 g of methanol are distilled off, which corresponds to approximately 84% of the theoretical amount. Then 205 g of n-butanol are added and a further 120 g of distillate are removed at a pressure of 150 mbar up to a bottom temperature of 123 ° C. A methanol concentration of only 0.011% can be determined.

    • Beispiel 4 (erfindungsgemäß): Example 4 (According to the Invention)

    Benötigt wird das Natriumsalz des 2-Amino-1-butanols in einem Gemisch aus 2-Amino-1-butanol und n-Butanol, es ist erforderlich, dass der Methanolgehalt möglichst klein ist:

  • 350 g (3,93 mol) 2-Amino-1-butanol werden mit 305 g (1,70 mol) Natrium-methanolat-Lösung (30 %ig in Methanol) versetzt. Bei einem Druck von 150 mbar werden 244 g Methanol abdestilliert, was ca. 90 % der theoretischen Menge entspricht. Anschließend werden 195 g n-Butanol zugegeben und bei einem Druck von 150 mbar weitere 120 g Destillat bis zu einer Sumpftemperatur von 114 °C abgenommen. Es kann eine Methanol-Konzentration von nur noch 0,010 % festgestellt werden.
    • The sodium salt of 2-amino-1-butanol is required in a mixture of 2-amino-1-butanol and n-butanol. It is necessary that the methanol content is as low as possible:
  • 350 g (3.93 mol) of 2-amino-1-butanol are mixed with 305 g (1.70 mol) of sodium methanolate solution (30% in methanol). At a pressure of 150 mbar, 244 g of methanol are distilled off, which corresponds to approximately 90% of the theoretical amount. Then 195 g of n-butanol are added and a further 120 g of distillate are removed at a pressure of 150 mbar up to a bottom temperature of 114 ° C. A methanol concentration of only 0.010% can be determined.

    • Beispiel 5 (Vergleichsbeispiel): Example 5 (comparative example ):

    Benötigt wird das Natriumsalz des 2-Amino-1-ethanols in einem Gemisch aus 2-Amino-1-ethanol und Toluol, es ist erforderlich, dass der Methanolgehalt möglichst klein ist:

  • 350 g (5,73 mol) 2-Amino-1-ethanol werden mit 92 g (1,70 mol) festem Natrium-methanolat versetzt. Bei einem Druck von 400 mbar werden an einer Kolonne mit 26 Trennstufen bis zu einer Sumpftemperatur von 171 °C 51 g Methanol abdestilliert, was ca. 94 % der theoretischen Menge entspricht. Bei weiterem Erwärmen des Sumpfes tritt deutliche Verfärbung auf. Anschließend werden 93 g Toluol zugegeben. Der Restmethanolgehalt beträgt 0,71%.
    • The sodium salt of 2-amino-1-ethanol is required in a mixture of 2-amino-1-ethanol and toluene. It is necessary that the methanol content is as low as possible:
  • 350 g (5.73 mol) of 2-amino-1-ethanol are mixed with 92 g (1.70 mol) of solid sodium methanolate. At a pressure of 400 mbar, 51 g of methanol are distilled off in a column with 26 separation stages up to a bottom temperature of 171 ° C., which corresponds to approximately 94% of the theoretical amount. If the sump is heated further, discolouration will appear. Then 93 g of toluene are added. The residual methanol content is 0.71%.

    • Beispiel 6 (Vergleichsbeispiel): Example 6 (comparative example ):

    Benötigt wird das Natriumsalz des 2-Amino-1-butanols in einem Gemisch aus 2-Amino-1-butanol und Toluol, es ist erforderlich, dass der Methanolgehalt möglichst klein ist:

  • 350 g (3,93 mol) 2-Amino-1-butanol werden mit 92 g (1,70 mol) festem Natrium-methanolat und 195 g Toluol versetzt. Bei einem Druck von 150 mbar werden an einer Kolonne mit 5 Trennstufen 171 g Destillat abdestilliert. Der Destillationssumpf fällt in Form einer homogenen Mischung an und weist einen Methanolgehalt von 2,22% auf.
    • The sodium salt of 2-amino-1-butanol is required in a mixture of 2-amino-1-butanol and toluene. It is necessary that the methanol content is as low as possible:
  • 350 g (3.93 mol) of 2-amino-1-butanol are mixed with 92 g (1.70 mol) of solid sodium methoxide and 195 g of toluene. At a pressure of 150 mbar, 171 g of distillate are distilled off in a column with 5 separation stages. The distillation bottoms are in the form of a homogeneous mixture and have a methanol content of 2.22%.

    • Claims (4)

    Verfahren zur Herstellung von Lösungen von Alkalimetallsalzen der allgemeinen Formel (I) MOYXR1 worin
    M steht für Li, Na, K, Rb oder Cs,
    Y steht für (C1-C8)-Alkylen,
    X steht für O, S, NR1,
    R1 steht für H, (C1-C8)-Alkyl, (C2-C8)-Alkenyl, (C2-C8)-Alkinyl, (C3-C8)-Cycloalkyl, (C6-C18)-Aryl, (C7-C19)-Aralkyl, (C3-C18)-Heteroaryl, (C4-C19)-Heteroaralkyl, ((C1-C8)-Alkyl)1-3-(C3-C8)-Cycloalkyl, ((C1-C8)-Alkyl)1-3-(C6-C18)-Aryl, ((C1-C8)-Alkyl)1-3-(C3-C18)-Heteroaryl,
    in einem Lösemittelgemisch aufweisend den korrespondierenden Alkohol der allgemeinen Formel (I) durch Umsetzung des korrespondieren Alkohols der allgemeinen Formel (I) mit dem entsprechenden Alkalimetallsalz eines Alkohols der allgemeinen Formel (II) MOR2 worin
    M die oben angegebene Bedeutung annimmt und
    R2 bedeutet Methyl, Ethyl, Propyl, Isopropyl, sec-, Iso- oder tert.-Butyl,
    oder durch Umsetzung des korrespondierenden Alkohols der allgemeinen Formel (I) mit dem entsprechenden Alkalimetallhydroxid,
    dadurch gekennzeichnet, dass eine Teilmenge des freigesetzten Alkohols der allgemeinen Formel (II) oder des freigesetzten Wassers zunächst ohne Zusatz eines Schleppmittels und anschließend die Restmenge unter Zuhilfenahme mindestens eines weiteren organischen Lösemittels als Schleppmittel aus der Reaktionsmischung destilliert wird.    Process for the preparation of solutions of alkali metal salts of the general formula (I) MOYXR 1 wherein
    M stands for Li, Na, K, Rb or Cs,
    Y represents (C 1 -C 8 ) alkylene,
    X stands for O, S, NR 1 ,
    R 1 represents H, (C 1 -C 8 ) alkyl, (C 2 -C 8 ) alkenyl, (C 2 -C 8 ) alkynyl, (C 3 -C 8 ) cycloalkyl, (C 6 - C 18 ) aryl, (C 7 -C 19 ) aralkyl, (C 3 -C 18 ) heteroaryl, (C 4 -C 19 ) heteroaralkyl, ((C 1 -C 8 ) alkyl) 1-3 - (C 3 -C 8 ) cycloalkyl, ((C 1 -C 8 ) alkyl) 1-3 - (C 6 -C 18 ) aryl, ((C 1 -C 8 ) alkyl) 1-3 - (C 3 -C 18 ) heteroaryl,
    in a solvent mixture comprising the corresponding alcohol of the general formula (I) by reacting the corresponding alcohol of the general formula (I) with the corresponding alkali metal salt of an alcohol of the general formula (II) MOR 2 wherein
    M assumes the meaning given above and
    R 2 denotes methyl, ethyl, propyl, isopropyl, sec-, iso- or tert-butyl,
    or by reacting the corresponding alcohol of the general formula (I) with the corresponding alkali metal hydroxide,
    characterized in that a portion of the liberated alcohol of the general formula (II) or the liberated water is first distilled from the reaction mixture without the addition of an entrainer and then the remainder with the aid of at least one further organic solvent as entrainer.         Verfahren nach Anspruch 1,
    dadurch gekennzeichnet, dass als weiteres organisches Lösemittel ein Schleppmittel ausgewählt wird aus der Gruppe bestehend aus linearen oder cyclischen aliphatischen Kohlenwasserstoffen, aromatischen Kohlenwasserstoffen, Verbindungen des Typs der allgemeinen Formel (III) R1(XY)nXR1 worin
    n = 1 oder 2 ist,
    R1 jeweils unabhängig voneinander, X jeweils unabhängig voneinander und Y die in Anspruch 1 angegebene Bedeutung annehmen,
    und Alkoholen der allgemeinen Formel (IV) R3OH worin
    R3 = (C4-C8)-Alkyl, (C2-C8)-Alkenyl, (C2-C8)-Alkinyl oder (C3-C8)-Cycloalkyl ist.    Method according to claim 1,
    characterized in that an entrainer is selected as a further organic solvent from the group consisting of linear or cyclic aliphatic hydrocarbons, aromatic hydrocarbons, compounds of the type of the general formula (III) R 1 (XY) n XR 1 wherein
    n = 1 or 2,
    R 1 in each case independently of one another, X in each case independently of one another and Y assume the meaning given in claim 1,
    and alcohols of the general formula (IV) R 3 OH wherein
    R 3 = (C 4 -C 8 ) alkyl, (C 2 -C 8 ) alkenyl, (C 2 -C 8 ) alkynyl or (C 3 -C 8 ) cycloalkyl.         Verfahren nach Anspruch 1 und/oder 2,
    dadurch gekennzeichnet, dass die Destillationen bei Drücken von 10 mbar bis 15 bar durchgeführt werden.    Method according to claim 1 and / or 2,
    characterized in that the distillations are carried out at pressures of 10 mbar to 15 bar.         Verfahren nach mindestens einem der vorhergehenden Ansprüche,
    dadurch gekennzeichnet, dass 10 - 90 Vol.-% des freigesetzten Alkohols (II) oder Wassers ohne Schleppmittel abdestilliert werden.    Method according to at least one of the preceding claims,
    characterized in that 10 - 90 vol .-% of the alcohol (II) or water released are distilled off without entrainer.
    EP03103465A 2002-11-12 2003-09-19 Process for the preparation of alkali metal salts of functionalised alcohols Expired - Lifetime EP1420007B1 (en)

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    CA2448839A1 (en) 2004-05-12
    US7273956B2 (en) 2007-09-25
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    US20040097759A1 (en) 2004-05-20
    ATE344229T1 (en) 2006-11-15
    CA2448839C (en) 2010-10-05
    IL158796A (en) 2009-11-18
    ES2276006T3 (en) 2007-06-16
    EP1420007B1 (en) 2006-11-02
    DE50305553D1 (en) 2006-12-14
    DE10252413A1 (en) 2004-05-27

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